JP2003346322A - Magnetic recording medium and its manufacturing method - Google Patents

Magnetic recording medium and its manufacturing method

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Publication number
JP2003346322A
JP2003346322A JP2002154942A JP2002154942A JP2003346322A JP 2003346322 A JP2003346322 A JP 2003346322A JP 2002154942 A JP2002154942 A JP 2002154942A JP 2002154942 A JP2002154942 A JP 2002154942A JP 2003346322 A JP2003346322 A JP 2003346322A
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JP
Japan
Prior art keywords
film
protective film
magnetic
carbon
recording medium
Prior art date
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Granted
Application number
JP2002154942A
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Japanese (ja)
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JP4603759B2 (en
Inventor
Shigehiko Fujimaki
成彦 藤巻
Toru Hachitsue
徹 八▲杖▼
Yuichi Kokado
雄一 小角
Toshinori Ono
俊典 大野
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Hitachi Ltd
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Hitachi Ltd
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Priority to JP2002154942A priority Critical patent/JP4603759B2/en
Priority to US10/377,678 priority patent/US7045175B2/en
Publication of JP2003346322A publication Critical patent/JP2003346322A/en
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Publication of JP4603759B2 publication Critical patent/JP4603759B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Magnetic Record Carriers (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem wherein a carbon protective film of fine tetrahedral structure having small loss of free energy is formed by the sub-plantation of carbon ion, when a cathodic arc vapor deposition is applied, but deterioration of magnetic characteristics occurs, even if thinning the protective film is achieved by the formation of fine and hard tetrahedral carbon because the incident carbon ion forms a mixed area at the interface of a recording magnetic film and the carbon protective film. <P>SOLUTION: A magnetic recording medium is provided with at least a base film, a recording magnetic film and a carbon-containing protective film formed on a disk-shaped base material. In this case, a multi-layer protective film is provided on the recording magnetic film, and accordingly, the protective film of lower layer blocks the incidence of the carbon ion to the recording magnetic film. As a result of this, the magnetic recording medium, having the hard protective film obtained by the cathodic arc vapor deposition which is superior in corrosion resistance and abrasion resistance, is provided with causing changes in the magnetic characteristics. <P>COPYRIGHT: (C)2004,JPO

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は磁気記録媒体の製造
方法に係り、特に、１平方インチ当り５０ギガビット以
上の高記録密度を可能とし、且つ、信頼性の高い磁気記
憶装置を実現するための磁気記録媒体、及びその製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a magnetic recording medium, and more particularly to a method for realizing a highly reliable magnetic storage device capable of achieving a high recording density of 50 gigabits per square inch or more. The present invention relates to a magnetic recording medium and a method for manufacturing the same.

【０００２】[0002]

【従来の技術】従来から知られている磁気記録媒体の製
造方法は、極めて平滑な非磁性基板上に少なくとも記録
磁性膜の結晶配向や粒径制御のためマグネトロン・スパ
ッタリング法でＣｒ、Ｃｒ−Ｖ、Ｃｒ−ＴｉなどのＣｒ
合金からなる下地膜と前記下地膜上にマグネトロン・ス
パッタリング法でＣｏＣｒＴａやＣｏＣｒＰｔなどの記
録磁性膜を磁化容易軸が基板と平行、もしくはほぼ平行
になるように形成する。記録磁性膜としては、この他に
垂直磁気異方性を有するＣｏ、Ｃｏ−Ｎｉや軟磁性材料
であるパーマロイ膜の上に形成されたＣｏ−Ｃｒなどの
垂直磁化膜などがある。さらにプラズマプロセスによる
物理的気相蒸着（ＰＶＤ）法、又は化学的気相蒸着（Ｃ
ＶＤ）法で炭素主体の保護膜を形成する。炭素膜の成長
過程では成膜方式による蒸着粒子エネルギーの違いが膜
物性に反映され、例えば、スパッタ粒子の平均エネルギ
ーは５ｅＶ程度であり、プラズマＣＶＤのガス種はさら
に低い０．０３ｅＶの熱運動エネルギー程度であるが、
基板バイアスにより炭化水素イオンが数百Vで加速され
る。一般に、低圧での低エネルギー蒸着粒子の表面堆積
では緻密なテトヘドラルカーボン構造は成長せず、とく
に炭化水素ラジカルの表面堆積ではポリマー重合する。
逆に、炭素イオンを加速して入射させると、膜内部に侵
入し、大きな内部圧力を受け自由エネルギー損失の小さ
い緻密なテトラヘドラル構造が成長する。しかし、過剰
のイオン入射エネルギーは熱に変換され、熱的に安定な
グラファイト・ライクなトリゴナル構造を成長させてし
まう。一方、アーク放電を利用したカソーディック・ア
ーク蒸着法ではグラファイト・カソードを用いること
で、５０〜７０ｅＶのエネルギーで炭素イオンを引き出
すことができ、硬く緻密な炭素膜（テトラヘドラル・カ
ーボン膜）の形成に適していることから磁気記録デバイ
スへの応用が期待されている。一般にカソーディック・
アーク蒸着法により形成されるテトラヘドラル・カーボ
ン膜は炭素価電子のsp3混成による結合比率が高く、質
量密度は２．５ｇ・ｃｍ−３以上になる。プラズマＣＶ
Ｄ法でもアセチレンを反応ガスにした電子サイクロトロ
ン共鳴を用いてイオンエネルギーを制御すれば高密度の
水素化炭素膜を形成できるが、質量密度は２．４ｇ・ｃ
ｍ−３までにしか上がらない。このようなカソーディッ
ク・アーク蒸着法によるテトラヘドラル・カーボン膜の
質量密度に関しては、Ferrari等によって"Density, sp3
fraction, and cross-sectional structure of amorph
ous carbon films determined by x-ray reflectivity
and electron energy-loss spectroscopy"(PHYSICAL RE
VIEW B, 62 (2000) pp.11089-11103)のなかで詳しく述
べられている。カソーディック・アーク蒸着において基
板に入射する炭素イオンのエネルギーＥiは素電荷、プ
ラズマポテンシャル、基板バイアス、初期イオンエネル
ギーをそれぞれe、Ｖp、Ｖb、Ｅoとして［式１］で示さ
れることがShi Xu等によって“Properties of carbon i
on deposited tetrahedral amorphouscarbon films as
a function of ion energy”(Journal of Applied Phys
ics,79 (1996) pp.7234-7240)のなかで詳しく記載され
ている。［式１］から電子温度が５ｅＶ〜１０ｅＶのプ
ラズマで浮遊電位（Ｖp−Ｖf）は２３Ｖ〜４６Ｖとな
り、アーク源で約２５ｅＶのエネルギーを得たＣ＋イオ
ンはフローティング基板に約５０〜７０ｅＶのエネルギ
ーに入射することになる。上記のフローティングポテン
シャルに関しては、Chapmanによる“GLOW DISCHARGE PO
CESS”（ John Wiley & Sons, Inc., New York 1980）
を原書とする“プラズマプロセシングの基礎”（電気書
院 1985年、第４７−６５項）の中で詳しく述べられて
いる。2. Description of the Related Art A conventionally known method of manufacturing a magnetic recording medium is to use a magnetron sputtering method to control the crystal orientation and grain size of at least a recording magnetic film on an extremely smooth nonmagnetic substrate. Cr, such as Cr-Ti
A recording magnetic film such as CoCrTa or CoCrPt is formed on the base film made of an alloy and on the base film by a magnetron sputtering method so that the axis of easy magnetization is parallel to or substantially parallel to the substrate. Other examples of the recording magnetic film include a perpendicular magnetic film such as Co, Co-Ni having perpendicular magnetic anisotropy, and Co-Cr formed on a permalloy film which is a soft magnetic material. Furthermore, physical vapor deposition (PVD) by a plasma process or chemical vapor deposition (C
A protective film mainly composed of carbon is formed by the VD) method. In the growth process of the carbon film, the difference in the deposition particle energy depending on the film formation method is reflected in the film physical properties. To the extent,
Hydrocarbon ions are accelerated at several hundred volts by the substrate bias. In general, a dense tetohedral carbon structure does not grow at the surface deposition of low energy deposition particles at low pressure, and polymer polymerization occurs particularly at the surface deposition of hydrocarbon radicals.
Conversely, when carbon ions are accelerated and incident, they penetrate into the film, receive a large internal pressure, and grow a dense tetrahedral structure with small free energy loss. However, the excess ion incident energy is converted to heat, which results in the growth of a thermally stable graphite-like trigonal structure. On the other hand, in the cathodic arc deposition method using arc discharge, carbon ions can be extracted with an energy of 50 to 70 eV by using a graphite cathode to form a hard and dense carbon film (tetrahedral carbon film). Because it is suitable, it is expected to be applied to magnetic recording devices. Generally cathodic
The tetrahedral carbon film formed by the arc evaporation method has a high bonding ratio due to sp3 hybridization of carbon valence electrons, and has a mass density of 2.5 g · cm −3 or more. Plasma CV
In method D, a high-density hydrogenated carbon film can be formed by controlling the ion energy using electron cyclotron resonance using acetylene as a reaction gas, but the mass density is 2.4 g · c.
m-3 only. Regarding the mass density of a tetrahedral carbon film formed by such a cathodic arc evaporation method, see Ferrari et al., "Density, sp3
fraction, and cross-sectional structure of amorph
ous carbon films determined by x-ray reflectivity
and electron energy-loss spectroscopy "(PHYSICAL RE
VIEW B, 62 (2000) pp.11089-11103). Shi Xu et al. Show that the energy Ei of carbon ions incident on a substrate in cathodic arc deposition is expressed by [Equation 1] as e, Vp, Vb, and Eo, respectively, as elementary charge, plasma potential, substrate bias, and initial ion energy. By “Properties of carbon i
on deposited tetrahedral amorphouscarbon films as
a function of ion energy ”(Journal of Applied Phys
ics, 79 (1996) pp.7234-7240). From [Equation 1], the floating potential (Vp-Vf) becomes 23 V to 46 V with the plasma having the electron temperature of 5 eV to 10 eV, and the C + ions obtained with the energy of about 25 eV by the arc source become the energy of about 50 to 70 eV on the floating substrate. Will be incident. Regarding the floating potential, see “GLOW DISCHARGE PO” by Chapman.
CESS ”(John Wiley & Sons, Inc., New York 1980)
The book is described in detail in "Basics of Plasma Processing" (Electric Publishing, 1985, pp. 47-65).

【０００３】[0003]

【式１】 Ｅi＝ｅ（Ｖp−Ｖb）+Ｅo 更に、このようなグラファイト・カソードのアーク放電
による炭素薄膜の作製とその応用技術についてはトライ
ボロジスト第４５巻１０号（２０００年）第７３９−７
４６項のなかで詳しく記載されている。炭素イオンは約
６０ｅＶのエネルギーでテトラヘドラル・カーボン膜に
入射すると約２原子層相当の０．４ｎｍ程度侵入する
が、成膜初期では質量数の大きいＣｏ等の金属原子に入
射するためエネルギー交換が少なく、金属磁性膜に０．
６５ｎｍ程度まで侵入してしまう。その結果、記録磁性
層の表面に０．６５ｎｍの厚さで混合領域が形成され
て、磁気特性が変化する欠点のあることがわかった。[Formula 1] Ei = e (Vp−Vb) + Eo Further, the production of such a carbon thin film by the arc discharge of a graphite cathode and its application technique are described in Tribologist, Vol. 45, No. 10, 2000 (No. 739). 7
It is described in detail in section 46. When carbon ions enter the tetrahedral carbon film with an energy of about 60 eV, they penetrate about 0.4 nm, which is equivalent to about 2 atomic layers. And 0.
It penetrates to about 65 nm. As a result, it was found that a mixed region was formed with a thickness of 0.65 nm on the surface of the recording magnetic layer, and there was a disadvantage that the magnetic characteristics changed.

【０００４】[0004]

【発明が解決しようとする課題】上記従来技術に述べら
れたカソーディク・アーク蒸着法を用いれば、炭素イオ
ンのサブ・プランテーションにより緻密なテトラヘドラ
ル構造の炭素保護膜を形成できるが、入射する炭素イオ
ンが記録磁性膜との界面に混合領域を形成し磁気特性を
変化させる問題があり、緻密で硬いテトラヘドラル・カ
ーボン保護膜を備えた磁気ディスクを作製しても、反っ
て磁気特性を劣化させる問題を発生するという欠点があ
った。By using the cathodic arc evaporation method described in the above prior art, a dense carbon protective film having a tetrahedral structure can be formed by sub-plantation of carbon ions. There is a problem of changing the magnetic characteristics by forming a mixed region at the interface with the recording magnetic film, and even if a magnetic disk with a dense and hard tetrahedral carbon protective film is manufactured, the problem of deteriorating magnetic characteristics occurs Had the disadvantage of doing so.

【０００５】そこで、本発明の目的は、上記の如く炭素
イオン入射により記録磁性膜で磁気特性が劣化するのを
阻止するため、保護膜を多層化したことを特徴とする磁
気記録媒体及びその製造方法を提供することである。Accordingly, an object of the present invention is to provide a magnetic recording medium having a multi-layered protective film in order to prevent the magnetic properties of the recording magnetic film from deteriorating due to the incidence of carbon ions as described above, and a method of manufacturing the same. Is to provide a way.

【０００６】[0006]

【課題を解決するための手段】本発明の磁気記録媒体
は、円板状の基材上に少なくとも下地膜、記録磁性膜、
保護膜からなる磁気記録媒体において、前記保護膜が前
記記録磁性膜上に形成された多層保護膜であって、最上
層のが質量密度２．５ｇ・ｃｍ-3以上の炭素膜であるこ
とを特徴とする。The magnetic recording medium of the present invention comprises at least a base film, a recording magnetic film,
In a magnetic recording medium comprising a protective film, the protective film is a multilayer protective film formed on the recording magnetic film, and the uppermost layer is a carbon film having a mass density of 2.5 gcm-3 or more. Features.

【０００７】また本発明の磁気記録媒体は、前記の多層
保護膜の最上層を除く少なくとも一層が最上層よりも質
量密度の低い厚さ０．２ｎｍ〜２ｎｍの炭素皮膜である
ことを特徴とする。The magnetic recording medium of the present invention is characterized in that at least one layer of the multilayer protective film except for the uppermost layer is a carbon film having a lower mass density than the uppermost layer and a thickness of 0.2 nm to 2 nm. .

【０００８】さらに本発明の磁気記録媒体の特徴は、前
記の多層保護膜の最上層を除く少なくとも一層が炭素に
少なくとも水素、窒素、硼素、珪素、フッ素の何れかを
含む厚さ０．２ｎｍ〜２ｎｍの皮膜から成ることにあ
る。Further, a feature of the magnetic recording medium of the present invention is that at least one layer except the uppermost layer of the above-mentioned multilayer protective film has a thickness of at least 0.2 nm containing at least one of hydrogen, nitrogen, boron, silicon and fluorine in carbon. It consists of a 2 nm film.

【０００９】また、本発明の磁気記録媒体の特徴は、前
記の多層保護膜の最上層を除く少なくとも一層が珪素、
又はその酸化物、窒化物、炭化物、若しくは硼素、又は
その酸化物、窒化物、炭化物、若しくは非磁性金属、又
はその酸化物、窒化物、炭化物から成る厚さ０．２ｎｍ
〜２ｎｍの皮膜とすることにある。The magnetic recording medium of the present invention is characterized in that at least one layer of the multilayer protective film except for the uppermost layer is made of silicon,
Or its oxide, nitride, carbide, or boron, or its oxide, nitride, carbide, or nonmagnetic metal, or its oxide, nitride, or carbide, having a thickness of 0.2 nm.
２2 nm.

【００１０】本発明の磁気記録媒体の製造方法は、円板
状の基材上に少なくとも下地膜、記録磁性膜、保護膜を
順次形成する工程を有する磁気記録媒体の製造方法に於
いて、前記保護膜が前記記録磁性膜上に形成された多層
保護膜であって、最上層の保護膜をアークプラズマ源か
ら引き出された炭素イオンの入射により形成することを
特徴とする。The method of manufacturing a magnetic recording medium according to the present invention comprises the step of sequentially forming at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate. A protective film is a multilayer protective film formed on the recording magnetic film, wherein the uppermost protective film is formed by incidence of carbon ions extracted from an arc plasma source.

【００１１】また、本発明の磁気記録媒体の製造方法
は、前記の多層保護膜の最上層を除く少なくとも一層に
厚さ０．２ｎｍ〜２ｎｍの炭素皮膜をマグネトロン・ス
パッタリング法、又はプラズマCVD法により形成するこ
とを特徴とする。Further, in the method for manufacturing a magnetic recording medium of the present invention, a carbon film having a thickness of 0.2 nm to 2 nm is formed on at least one layer other than the uppermost layer of the multilayer protective film by a magnetron sputtering method or a plasma CVD method. It is characterized by forming.

【００１２】さらに、本発明の磁気記録媒体の製造方法
は、前記の多層保護膜の最上層を除く少なくとも一層に
炭素に水素、窒素、硼素、珪素、フッ素の何れかを含む
厚さ０．２ｎｍ〜２ｎｍの皮膜をマグネトロン・スパッ
タリング法、又はプラズマCVD法により形成すること特
徴とする。本発明の磁気記録媒体の製造方法は、前記の
多層保護膜の最上層を除く少なくとも一層に珪素、又は
その酸化物、窒化物、炭化物、若しくは硼素、又はその
酸化物、窒化物、炭化物、若しくは非磁性金属、又はそ
の酸化物、窒化物、炭化物から成る厚さ０．２ｎｍ〜２
ｎｍの皮膜をマグネトロン・スパッタリング法、又はプ
ラズマCVD法により形成することを特徴とする。本発明
の磁気記録媒体の製造方法は、円板状の基材上に少なく
とも下地膜、記録磁性膜、保護膜からなる磁気記録媒体
の製造方法に於いて、前記記録磁性膜上に保護膜をアー
クプラズマ源から引き出された炭素イオンの入射により
形成する成膜工程で成膜開始から一定時間だけ基板に正
バイアスを加えることを特徴とする。また、本発明の磁
気記録媒体の製造方法は、円板状の基材上に少なくとも
下地膜、記録磁性膜、保護膜からなる磁気記録媒体の製
造方法に於いて、前記記録磁性膜上に保護膜をアークプ
ラズマ源から引き出された炭素イオンの入射により形成
する成膜工程で成膜開始から一定時間だけメタン、エタ
ン、プロパン、ブタン、エチレン、プロピレン、ブチレ
ン、アセチレン、トルエン等の炭化水素ガスを供給する
ことを特徴とする。Further, according to the method of manufacturing a magnetic recording medium of the present invention, at least one layer other than the uppermost layer of the above-mentioned multilayer protective film has a thickness of 0.2 nm containing carbon containing any of hydrogen, nitrogen, boron, silicon and fluorine. A film having a thickness of 2 nm is formed by a magnetron sputtering method or a plasma CVD method. In the method for manufacturing a magnetic recording medium of the present invention, at least one layer other than the uppermost layer of the multilayer protective film includes silicon, or an oxide, nitride, carbide, or boron thereof, or an oxide, nitride, carbide, or Non-magnetic metal or a thickness of 0.2 nm to 2 made of an oxide, nitride or carbide thereof
The film is characterized by being formed by a magnetron sputtering method or a plasma CVD method. The method for producing a magnetic recording medium of the present invention is a method for producing a magnetic recording medium comprising at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate, wherein a protective film is formed on the recording magnetic film. In a film forming process formed by incidence of carbon ions extracted from an arc plasma source, a positive bias is applied to the substrate for a certain period of time from the start of film formation. Further, the method of manufacturing a magnetic recording medium of the present invention is a method of manufacturing a magnetic recording medium comprising at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate. In a film forming process in which a film is formed by the incidence of carbon ions extracted from an arc plasma source, hydrocarbon gas such as methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, and toluene is emitted for a certain period of time from the start of film formation. It is characterized by supplying.

【００１３】次に、上記構成について機能的に説明す
る。上記構成の磁気記録媒体では、多層保護膜が磁性膜
に積層されるのでアークイオン源から引き出された炭素
イオンが約６０ｅＶのエネルギーで入射しても、多層保
護膜でのエネルギー損失により記録磁性膜まで到達、又
は、界面下に侵入せず、磁気特性の変動を阻止できる。
すなわち、記録磁性膜と多層保護膜の最下層との界面で
混合領域の形成を防止するのに有効である。入射粒子エ
ネルギーは入射粒子と標的粒子が同じ場合に最も良く伝
達され、炭素皮膜が最上層を除く少なくとも一層にあれ
ばイオン阻止能が高く下層保護膜を薄くできるので望ま
しいが、最上層を除く少なくとも一層が炭素に少なくと
も水素、窒素、硼素、珪素、フッ素の何れかを含む皮膜
や珪素、又はその酸化物、窒化物、若しくは非磁性金
属、又はその酸化物、窒化物、炭化物から成る皮膜であ
ってもよい。例えば、密度２g/cm3の炭素皮膜をスパッ
タ蒸着した場合、多層保護膜の最上層を除く少なくとも
一層の厚さが０．５ｎｍあれば、約６０ｅＶのエネルギ
ーで入射する炭素イオンは阻止されて記録磁性膜に侵入
しない。その他の原子から構成された皮膜でも、原子
数、質量数及び密度に応じて膜厚を適正化すれば入射炭
素イオンの侵入を阻止できる。多層保護膜の最上層を除
く少なくとも一層の厚さは１原子層相当の０．２ｎｍ以
上であれば入射イオンの減速効果があらわれるが、記録
磁性膜への侵入を阻止するには２原子層相当以上が必要
である。しかし、下層膜を厚くすると磁気スペーシング
が広がる欠点があり、一方、多層保護膜の最上層の薄膜
化は磁気記録媒体の耐摺動性を劣化させるため、最上層
を除く下層膜は1nm以上となる膜厚を上限とするのが望
ましい。多層保護膜の厚さを３ｎｍ以下とするならば、
最上層を除く下層の厚さは０．２ｎｍ〜２ｎｍの範囲と
する必要がある。Next, the above configuration will be functionally described. In the magnetic recording medium having the above configuration, since the multilayer protective film is laminated on the magnetic film, even if carbon ions extracted from the arc ion source enter with an energy of about 60 eV, the recording magnetic film is lost due to energy loss in the multilayer protective film. , Or does not penetrate under the interface, thereby preventing fluctuations in magnetic properties.
That is, it is effective to prevent formation of a mixed region at the interface between the recording magnetic film and the lowermost layer of the multilayer protective film. The incident particle energy is best transmitted when the incident particle and the target particle are the same, and it is desirable that the carbon coating is provided in at least one layer except for the uppermost layer since the ion stopping power is higher and the lower protective film can be thinned, but at least except for the uppermost layer. One layer is a film containing at least one of hydrogen, nitrogen, boron, silicon, and fluorine in carbon, and a film made of silicon, or an oxide, nitride, or nonmagnetic metal thereof, or an oxide, nitride, or carbide thereof. You may. For example, when a carbon film having a density of 2 g / cm3 is sputter-deposited, if the thickness of at least one layer excluding the uppermost layer of the multilayer protective film is 0.5 nm, incident carbon ions with an energy of about 60 eV are blocked and the recording magnetic property is reduced. Does not penetrate the membrane. Even if the film is composed of other atoms, the penetration of incident carbon ions can be prevented by optimizing the film thickness in accordance with the number of atoms, the mass number and the density. If the thickness of at least one layer other than the uppermost layer of the multilayer protective film is 0.2 nm or more, which is equivalent to one atomic layer, a deceleration effect of incident ions appears, but in order to prevent penetration into the recording magnetic film, two atomic layers are required. The above is necessary. However, thickening the lower layer film has the disadvantage of expanding the magnetic spacing.On the other hand, reducing the thickness of the uppermost layer of the multilayer protective film deteriorates the sliding resistance of the magnetic recording medium. It is desirable that the upper limit of the film thickness is set as the upper limit. If the thickness of the multilayer protective film is 3 nm or less,
The thickness of the lower layer excluding the uppermost layer needs to be in the range of 0.2 nm to 2 nm.

【００１４】[0014]

【発明の実施の形態】以下、図面を参照して本発明の実
施の形態を説明する。図１は本発明の特徴を最もよく表
している磁気ディスクの断面構成図、図２は本発明の実
施例に示すカソーディック・アーク蒸着装置を備えた磁
気記ディスク製造設備の構成図、図３は本発明の実施例
及び比較例に示すカソーディック・アーク蒸着装置の構
成図、図４は本発明の比較例１に示す磁気記ディスクの
断面構成図、図５は本発明の比較例２に示す磁気記ディ
スクの断面構成図、図６は本発明の実施例および比較例
に示す磁気記録媒体で測定したラマンスペクトルの比
較、図７は本発明に係わる核阻止能計算によるＣｏ膜に
入射する炭素イオンと入射エネルギーの関係図、図８は
本発明に係わる核阻止能計算による炭素膜に入射する炭
素イオンと入射エネルギーの関係図、図９は本発明に係
わる入射原子と標的原子のエネルギー伝達の相関、図１
０は本発明の実施例２に示す磁気ディスクの断面構成
図、図１１は本発明の実施例３に示す磁気ディスクの断
面構成図、表１は本発明の実施例１と比較例１、２に示
す磁気ディスクの磁気特性の比較、表２は本発明の実施
例２、３と比較例１に示す磁気ディスクの磁気特性の比
較、表３は本発明の実施例４、５と比較例１に示す磁気
ディスクの磁気特性の比較である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional configuration diagram of a magnetic disk that best illustrates the features of the present invention. FIG. 2 is a configuration diagram of a magnetic recording disk manufacturing facility equipped with a cathodic arc evaporation apparatus according to an embodiment of the present invention. FIG. 4 is a configuration diagram of a cathodic arc evaporation apparatus shown in Examples and Comparative Examples of the present invention, FIG. 4 is a sectional configuration diagram of a magnetic recording disk shown in Comparative Example 1 of the present invention, and FIG. 5 is Comparative Example 2 of the present invention. FIG. 6 is a cross-sectional configuration diagram of a magnetic recording disk shown in FIG. 6, FIG. 6 is a comparison of Raman spectra measured on magnetic recording media shown in Examples of the present invention and Comparative Examples, and FIG. 7 is incident on a Co film by nuclear stopping power calculation according to the present invention. FIG. 8 is a diagram showing the relationship between carbon ions and incident energy according to the present invention, FIG. 8 is a diagram showing the relationship between carbon ions incident on the carbon film by the nuclear stopping power calculation and the incident energy according to the present invention, and FIG. Correlation, Figure 1
0 is a cross-sectional configuration diagram of a magnetic disk according to a second embodiment of the present invention, FIG. 11 is a cross-sectional configuration diagram of a magnetic disk according to a third embodiment of the present invention, and Table 1 is a first embodiment of the present invention and comparative examples 1 and 2. Table 2 shows a comparison of the magnetic characteristics of the magnetic disks shown in Examples 2 and 3 of the present invention and Comparative Example 1, and Table 3 shows a comparison of the magnetic characteristics of the magnetic disks shown in Examples 1 and 2. 3 is a comparison of the magnetic characteristics of the magnetic disks shown in FIG.

【００１５】［実施例1］図１に示す構成の磁気ディス
クを図３のカソーディック・アーク蒸着装置を備えた図
２の磁気ディスク製造設備により作製した。本実施例の
磁気ディスクは、ガラス製のディスク状基体１にマグネ
トロン・スパッタリングにより膜厚が１０ｎｍのＮｉＣ
ｒ系プリコード膜２と、膜厚が２０ｎｍのＣｒ合金下地
膜３と、膜厚が２５ｎｍのＣｏＣｒ系合金の記録磁性膜
４と、膜厚が０．５ｎｍの炭素薄膜を下層保護膜５とし
て順次成膜し、更にカソーディック・アーク蒸着により
上層保護膜６を膜厚１．５ｎｍで積層してある。この磁
気ディスクの磁気特性とラマンスペクトルを測定した。
本実施例におけるラマンスペクトルの測定結果は、図６
に図示されるグラフ２８である。図２の磁気ディスク製
造設備はマグネトロン・スパッタリング電極９ａ〜９ｃ
と共に図３のカソーディック・アーク蒸着装置１１を搭
載し、上層保護膜６を除く各層が下層保護膜５を含めて
マグネトロン・スパッタリングにより形成される。一
方、図２のカソーディック・アーク蒸着装置はアーク・
プラズマ源１３と、成膜室１４と、ダクト１５と成膜室
１４内に置かれた基板１６と、ダクト１５と成膜室１４
の結合部に設けられた電磁偏向器１７から構成され、上
層保護膜６の成膜に用いた。この装置では、前記のアー
クプラズマ源１３内にある可動アノード１８がグラファ
イトロッドのカソード１９に接触することでアーク放電
を発生し、そのときにアークプラズマ源１３から飛び出
す炭素イオンがダクト１５を介して成膜室１４の基板１
６に入射し、炭素皮膜を作製する。基板１６は電気的に
浮遊したホルダー２３に保持される。基板１６には電源
２４によりバイアスを印加することが可能であるが、本
実施例では、バイアスは印加せず動作時の基板は浮遊電
位とした。Example 1 A magnetic disk having the structure shown in FIG. 1 was produced by the magnetic disk manufacturing equipment shown in FIG. 2 equipped with the cathodic arc evaporation apparatus shown in FIG. The magnetic disk according to the present embodiment has a thickness of 10 nm formed on a glass disk-shaped substrate 1 by magnetron sputtering.
An r-based pre-code film 2, a Cr alloy base film 3 with a thickness of 20 nm, a recording magnetic film 4 of a CoCr-based alloy with a thickness of 25 nm, and a carbon thin film with a thickness of 0.5 nm as the lower protective film 5. Films are sequentially formed, and an upper protective film 6 having a thickness of 1.5 nm is further laminated by cathodic arc evaporation. The magnetic characteristics and Raman spectrum of this magnetic disk were measured.
The measurement result of the Raman spectrum in this embodiment is shown in FIG.
Is a graph 28 shown in FIG. The magnetic disk manufacturing equipment of FIG. 2 includes magnetron sputtering electrodes 9a to 9c.
At the same time, the cathodic arc evaporation apparatus 11 of FIG. 3 is mounted, and each layer except the upper protective film 6 is formed by magnetron sputtering including the lower protective film 5. On the other hand, the cathodic arc deposition apparatus of FIG.
A plasma source 13, a deposition chamber 14, a duct 15 and a substrate 16 placed in the deposition chamber 14, a duct 15 and a deposition chamber 14
, And was used for forming the upper protective film 6. In this apparatus, the movable anode 18 in the arc plasma source 13 contacts the cathode 19 of the graphite rod to generate an arc discharge. At that time, carbon ions jumping out of the arc plasma source 13 pass through the duct 15. Substrate 1 in deposition chamber 14
6 to form a carbon film. The substrate 16 is held by an electrically floating holder 23. Although a bias can be applied to the substrate 16 by the power supply 24, in this embodiment, no bias was applied and the substrate during operation was set to a floating potential.

【００１６】本実施の形態により、最上層の上層保護膜
６を質量密度２．５ｇ・ｃｍ-3以上の炭素膜とすること
ができ、プラズマＣＶＤ法によって形成される炭素膜よ
りも保護特性（耐蝕性や耐摩耗性）の良い保護膜を形成
することができる。また、本実施の形態における下層保
護膜５と上層保護膜６は、双方とも炭素を用いた炭素膜
であるが、形成方法の違いにより質量密度が異なるた
め、その質量密度の違いに応じて、層を対応付けて識別
する。 ［比較例１］実施例１においてアルゴンガスに窒素ガス
を１０％混合した１．３Ｐａの雰囲気でグラファイト・
カソード１９のマグネトロンスパッタ・スパッタリング
により２ｎｍの膜厚で窒素化炭素膜のみを保護膜２５と
して直接記録磁性膜４上に形成し、磁気特性と保護膜の
ラマンスペクトルを測定した。本比較例におけるラマン
スペクトルの測定結果は、図６に図示されるグラフ２９
である。図４は本比較例に示す磁気ディスクの断面構成
図である。 ［比較例２］実施例１において保護膜を多層にせず、カ
ソーディック・アーク蒸着により炭素膜２６のみを２ｎ
ｍの膜厚で記録磁性膜４上に直接積層し、図５に示す断
面構成の磁気ディスクを作製して磁気特性とラマンスペ
クトルを測定した。本比較例におけるラマンスペクトル
の測定結果は、図６に図示されるグラフ２７である。According to the present embodiment, the uppermost protective film 6 of the uppermost layer can be made of a carbon film having a mass density of 2.5 g · cm −3 or more. A protective film having good corrosion resistance and wear resistance can be formed. The lower protective film 5 and the upper protective film 6 in the present embodiment are both carbon films using carbon, but have different mass densities due to different forming methods. Identify and identify layers. [Comparative Example 1] In Example 1, graphite was mixed in an atmosphere of 1.3 Pa in which nitrogen gas was mixed at 10% with argon gas.
Only a carbon nitride film having a thickness of 2 nm was directly formed as a protective film 25 on the recording magnetic film 4 by magnetron sputtering / sputtering of the cathode 19, and the magnetic characteristics and Raman spectrum of the protective film were measured. The measurement result of the Raman spectrum in this comparative example is shown in a graph 29 in FIG.
It is. FIG. 4 is a cross-sectional configuration diagram of the magnetic disk shown in this comparative example. [Comparative Example 2] In Example 1, the protective film was not multilayered, and only the carbon film 26 was formed by cathodic arc evaporation to a thickness of 2n.
A magnetic disk having a sectional structure shown in FIG. 5 was fabricated by directly laminating the recording magnetic film 4 with a film thickness of m, and the magnetic characteristics and Raman spectrum were measured. The measurement result of the Raman spectrum in this comparative example is a graph 27 illustrated in FIG.

【００１７】[0017]

【表１】 [Table 1]

【００１８】実施例１、比較例１及び２に示す各磁気デ
ィスクの磁気特性は表１に示す通り、実施例１と比較例
１とでほぼ一致したのに対し、保護膜を多層化せずにカ
ソーディック・アーク蒸着により炭素膜２４のみを記録
磁性膜４上に直接形成した比較例２では、角型比Ｓ*及
び残留磁化Ｍｒと磁性層膜厚δの積Ｍｒ・δがそれぞれ
３．５％、５％減少し、保磁力Ｈｃが４％上昇した。一
方、図６に示すラマンスペクトルの比較では、記録磁性
膜４上の炭素皮膜に由来するラマンスペクトルが実施例
１（測定グラフ２８）と比較例２（測定グラフ２７）で
ほぼ同じ所謂テトラヘドラル・カーボン構造に特有な形
状なのに対し、比較例１（測定グラフ２９）では１４０
０cm-1付近の所謂Ｄバンドのピーク強度が高くスパッタ
蒸着カーボン膜に特有な形状であった。比較例２におけ
る炭素膜２６について高分解ラザフォード後方散乱分析
法の測定結果に基づき計算した質量密度は２．８ｇ・ｃ
ｍ−３であった。As shown in Table 1, the magnetic characteristics of the magnetic disks shown in Example 1 and Comparative Examples 1 and 2 were almost the same between Example 1 and Comparative Example 1, but the protective film was not multilayered. In Comparative Example 2 in which only the carbon film 24 was directly formed on the recording magnetic film 4 by cathodic arc evaporation, the squareness ratio S * and the product Mr · δ of the residual magnetization Mr and the magnetic layer thickness δ were respectively 3. The coercive force Hc decreased by 5% and 5%, and increased by 4%. On the other hand, in the comparison of the Raman spectra shown in FIG. 6, the so-called tetrahedral carbon whose Raman spectrum derived from the carbon film on the recording magnetic film 4 is almost the same in Example 1 (measurement graph 28) and Comparative Example 2 (measurement graph 27). In contrast to the shape peculiar to the structure, in Comparative Example 1 (measurement graph 29), 140
The peak intensity of the so-called D band near 0 cm -1 was high and the shape was peculiar to the sputter-deposited carbon film. The mass density of the carbon film 26 in Comparative Example 2 calculated based on the measurement result of the high-resolution Rutherford backscattering analysis method is 2.8 g · c.
m-3.

【００１９】以上から、アークプラズマ源１３から引き
出される炭素イオン入射により上層保護膜６を形成すれ
ば、実施例１の如く磁気特性は変化せず、下層保護膜５
は記録磁性膜４に入射する炭素イオンの侵入阻止に有効
であり、且つ、下層保護膜を０．５ｎｍの膜厚で設けて
も記録磁性膜４上に積層した炭素皮膜の化学構造に殆ど
影響しなかった。一般にアークプラズマ源１３から引き
出されるイオンのエネルギーは主にターゲット材質によ
り決まり、グラファイト・カソード１９から放出される
炭素イオン1個のエネルギーが約６０ｅＶでＣｏ膜に入
射したとして、核阻止能計算すると深さ０．６２ｎｍま
で侵入するのに対して（図７参照）、炭素膜への侵入深
さは０．４ｎｍとなる（図８参照）。それ故、厚さ０．
５ｎｍの炭素膜を下層保護膜５とすれば、炭素イオンは
下層保護膜５を貫いて記録磁性膜に到達、又は侵入しな
くなる。核阻止能計算では、皮膜への入射原子が膜を構
成する標的原子と間でトーマス・フェルミ・ポテンシャ
ルを仮定したクーロン力によりエネルギーを失うまで皮
膜内部に侵入するとした。図７，８はそれぞれ核阻止能
計算によるＣｏ膜及び炭素膜に入射する炭素イオンと入
射エネルギーの関係である。As described above, if the upper protective film 6 is formed by the incidence of carbon ions extracted from the arc plasma source 13, the magnetic characteristics do not change as in the first embodiment, and the lower protective film 5
Is effective in preventing the intrusion of carbon ions incident on the recording magnetic film 4, and even if the lower protective film is provided with a thickness of 0.5 nm, the chemical structure of the carbon film laminated on the recording magnetic film 4 is hardly affected. Did not. Generally, the energy of the ions extracted from the arc plasma source 13 is mainly determined by the target material. Assuming that the energy of one carbon ion emitted from the graphite cathode 19 is incident on the Co film at about 60 eV, the nuclear stopping power is calculated. The penetration depth reaches 0.42 nm (see FIG. 7), whereas the penetration depth into the carbon film is 0.4 nm (see FIG. 8). Therefore, a thickness of 0.
If the carbon film having a thickness of 5 nm is used as the lower protective film 5, carbon ions do not reach or enter the recording magnetic film through the lower protective film 5. In the calculation of nuclear stopping power, it was assumed that atoms incident on the film penetrate into the film until they lose energy by Coulomb force assuming Thomas-Fermi potential between the target atoms and the film. 7 and 8 show the relationship between the incident energy and the carbon ions incident on the Co film and the carbon film, respectively, based on the nuclear stopping power calculation.

【００２０】また、1回の衝突で入射原子から標的原子
に変換されるエネルギーはエネルギー伝達関数により表
され、炭素原子との衝突により変換されるエネルギーは
図９に示す関係にあって、入射する炭素原子よりも質量
数の大きいＣｏ原子との衝突ではエネルギーの変換が小
さく、炭素イオンの侵入は深くなる。通常、混合層の厚
さを定量するにはオージェー電子分光法による深さ方向
の分析が用いられるが、1次電子の非弾性衝突による平
均自由行程から推定される２次電子の脱出深さは１．５
〜２ｎｍであるため、混合層がそれ以下で薄い場合は定
量が容易でない。このようなオージェー電子分光法での
２次電子脱出深さと１次電子エネルギーの関係について
は山科俊郎、福田伸による“表面分析の基礎と応用”
（東京大学出版会 １９９１年、第５６−６４項）のな
かで詳しく記載されている。このため磁気特性（Ｍｒ
δ）の変化が記録磁性膜の膜厚減少に起因すると仮定
し、これから混合層の厚さを見積もると０．６ｎｍとな
り、図７に示す核阻止能計算による侵入深さ０．６２ｎ
ｍとほぼ一致した。即ち、実施例１に示す下層保護膜５
は、核阻止能計算で示した通り、カソーディク・アーク
蒸着による炭素イオンの記録磁性膜４への入射を阻止す
るのに有効で、この下層保護膜５を備えることで磁気特
性を変化させることなく硬く耐蝕性と耐摩耗性に優れた
保護膜を備えた磁気記録媒体を提供できる。勿論、実施
例１で基板を負バイアスすると、印加するバイアス電圧
によりイオンが加速されるので下層保護膜を厚くしない
と記録磁性膜４に入射する炭素イオンの侵入を阻止でき
ない。このような基板バイアスはイオンのエネルギー制
御に有効であるが、過剰のイオン入射エネルギーは熱に
変換され、熱的に安定なグラファイト・ライクなトリゴ
ナル構造を成長させてしまう。例えば、グラファイト・
カソード１９から放出され、基板１６に入射する炭素イ
オン1個のエネルギーは約６０ｅＶであり、これを負バ
イアスで基板に加速して炭素膜を形成したところ、−４
００Ｖ以上のバイアス電圧で炭素膜のラマンスペクトル
における所謂Ｄバンドの相対強度が急増した。すなわ
ち、炭素イオンの入射エネルギーを４６０ｅＶ以上にま
で加速するとテトラヘドラル炭素構造の成長が妨げら
れ、膜構造の強度は劣化する。図８からエネルギーが４
６０ｅＶの炭素イオンの入射による侵入深さは２ｎｍで
ある。よって、有効な基板の負バイアスである４００Ｖ
以下に対応して作製される下層保護膜の上限膜厚は２ｎ
ｍである。The energy converted from an incident atom to a target atom in one collision is represented by an energy transfer function, and the energy converted by a collision with a carbon atom has the relationship shown in FIG. In a collision with a Co atom having a larger mass number than a carbon atom, the conversion of energy is small, and the penetration of carbon ions is deep. Normally, depth analysis by Auger electron spectroscopy is used to quantify the thickness of the mixed layer, but the escape depth of secondary electrons estimated from the mean free path due to inelastic collision of primary electrons is 1.5
Since it is 〜2 nm, if the mixed layer is thinner than that, it is not easy to determine the amount. For the relationship between the secondary electron escape depth and the primary electron energy in Auger electron spectroscopy, Toshiro Yamashina and Shin Fukuda, "Basics and Application of Surface Analysis"
(The University of Tokyo Press, 1991, paragraphs 56-64). Therefore, the magnetic properties (Mr
It is assumed that the change in δ) is caused by a decrease in the thickness of the recording magnetic film. From this, the thickness of the mixed layer is estimated to be 0.6 nm, and the penetration depth is 0.62 n by the nuclear stopping power calculation shown in FIG.
and almost coincided with m. That is, the lower protective film 5 shown in the first embodiment
Is effective for preventing the incidence of carbon ions into the recording magnetic film 4 by cathodic arc evaporation as shown in the nuclear stopping power calculation, and by providing this lower protective film 5, the magnetic properties are not changed. It is possible to provide a magnetic recording medium having a hard, corrosion-resistant and abrasion-resistant protective film. Of course, when the substrate is negatively biased in the first embodiment, ions are accelerated by the applied bias voltage. Therefore, the penetration of carbon ions incident on the recording magnetic film 4 cannot be prevented unless the lower protective film is thickened. Although such a substrate bias is effective in controlling the energy of ions, excessive ion incident energy is converted into heat, and a thermally stable graphite-like trigonal structure grows. For example, graphite
The energy of one carbon ion emitted from the cathode 19 and incident on the substrate 16 is about 60 eV, and this is accelerated by a negative bias to the substrate to form a carbon film.
At a bias voltage of 00 V or more, the so-called D band relative intensity in the Raman spectrum of the carbon film sharply increased. That is, when the incident energy of the carbon ions is accelerated to 460 eV or more, the growth of the tetrahedral carbon structure is hindered, and the strength of the film structure deteriorates. From Fig. 8, the energy is 4
The penetration depth due to the incidence of 60 eV carbon ions is 2 nm. Therefore, the effective substrate negative bias of 400 V
The upper limit film thickness of the lower protective film produced corresponding to the following is 2n
m.

【００２１】なお、実施例１では記録磁性膜がＣｒ合金
を下地膜とした面内磁気異方性を有するＣｏＣｒ系合金
であったが、垂直磁気異方性を有するＣｏ、ＣｏＮｉ系
合金や軟磁性材料であるパーマロイ膜などの上に形成さ
れたＣｏＣｒ系合金などの垂直磁化膜、及びＣｏ等の磁
性層とＰｄ等の非磁性層を交互に積層した人工格子多層
膜であっても、実施例１に示した如く、下層保護膜がカ
ソーディク・アーク蒸着による成膜工程で炭素イオンの
記録磁性膜４への入射を阻止するのに有効であることは
勿論である。例えば、厚さ２００ｎｍの鉄ニッケル軟磁
性層下地層で裏打ちした厚さ２０nmのＣｏ−Ｃｒ垂直磁
気異方性層上にマグネトロン・スパッタリング法による
炭素皮膜を下層保護膜として形成してからカソーディッ
ク・アーク蒸着で上層保護膜となる炭素皮膜を形成した
場合、Ｃｏ−Ｃｒ垂直磁気異方性層に直接カソーディッ
ク・アーク蒸着により炭素保護膜を形成した場合に比べ
て、垂直磁気ディスク膜面に垂直な方向に測った保磁力
が５％上昇した。即ち、垂直磁気ディスクであっても保
護膜を二層化しないと、カソーディック・アーク蒸着に
よる炭素イオン入射によりＣｏ−Ｃｒ垂直磁気異方性層
等に炭素原子が侵入して磁気特性を変動させた。In the first embodiment, the recording magnetic film is a CoCr-based alloy having an in-plane magnetic anisotropy using a Cr alloy as a base film. Even if it is a perpendicular magnetization film such as a CoCr-based alloy formed on a magnetic material such as a permalloy film, or an artificial lattice multilayer film in which a magnetic layer such as Co and a non-magnetic layer such as Pd are alternately laminated. As shown in Example 1, it is needless to say that the lower protective film is effective to prevent the carbon ions from being incident on the recording magnetic film 4 in the film formation process by cathodic arc evaporation. For example, a carbon film is formed as a lower protective film by magnetron sputtering on a 20 nm thick Co—Cr perpendicular magnetic anisotropic layer lined with a 200 nm thick iron-nickel soft magnetic layer underlayer, In the case where a carbon film serving as an upper protective film is formed by arc evaporation, the carbon film is perpendicular to the perpendicular magnetic disk film surface, compared to the case where a carbon protective film is formed directly on the Co-Cr perpendicular magnetic anisotropic layer by cathodic arc evaporation. The coercive force measured in various directions increased by 5%. That is, even if it is a perpendicular magnetic disk, if the protective film is not formed into two layers, carbon atoms enter the Co-Cr perpendicular magnetic anisotropic layer and the like due to the incidence of carbon ions by cathodic arc evaporation, causing the magnetic characteristics to fluctuate. Was.

【００２２】［実施例２］実施例１における下層保護膜
５として膜厚が０．５ｎｍの窒素化炭素膜３０を備えた
磁気ディスクを図１０に示す断面構成図で作製し、磁気
特性を測定した。この窒素化炭素膜３０はアルゴンガス
に窒素ガスを１０％混合した１．３Ｐａの雰囲気でグラ
ファイト・カソードのマグネトロン・スパッタリングに
より形成した。上層保護膜６の形成は、実施例１と同様
のカソーディック・アーク蒸着法で実施した。[Embodiment 2] A magnetic disk provided with a 0.5 nm-thick nitrogenated carbon film 30 as the lower protective film 5 in Embodiment 1 was fabricated in a sectional view shown in FIG. 10, and the magnetic characteristics were measured. did. The nitrogenated carbon film 30 was formed by magnetron sputtering of a graphite cathode in an atmosphere of 1.3 Pa in which nitrogen gas was mixed with argon gas at 10%. The upper protective film 6 was formed by the same cathodic arc deposition method as in Example 1.

【００２３】［実施例３］実施例１における下層保護膜
５として膜厚が０．５ｎｍの珪素含有炭素膜３１を備え
た磁気ディスクを図１１に示す断面構成図で作製し、磁
気特性を測定した。この珪素含有炭素膜３１は２０ａｔ
％の珪素を含むグラファイト・ターゲットによりマグネ
トロン・スパッタリングで形成した。上層保護膜６の形
成は、実施例１と同様のカソーディック・アーク蒸着法
で実施した。[Embodiment 3] A magnetic disk provided with a silicon-containing carbon film 31 having a thickness of 0.5 nm as the lower protective film 5 in the embodiment 1 was manufactured with the sectional configuration diagram shown in FIG. 11, and the magnetic characteristics were measured. did. This silicon-containing carbon film 31 has a thickness of 20 at.
% Was formed by magnetron sputtering using a graphite target containing silicon. The upper protective film 6 was formed by the same cathodic arc deposition method as in Example 1.

【００２４】[0024]

【表２】 [Table 2]

【００２５】この結果、実施例２、３に示す磁気ディス
クの磁気特性は、共に表２に示す如く比較例１の結果と
ほぼ一致し、すなわち、実施例１で示したカソーディッ
ク・アーク蒸着法による磁気特性と同様であることが分
かった。これにより、実施例２、３においても、上記の
窒素化炭素膜、珪素含有炭素膜が下層保護膜としてカソ
ーディック・アーク蒸着による成膜工程で炭素イオンの
記録磁性膜４への侵入を阻止するのに有効であることが
判明した。As a result, the magnetic characteristics of the magnetic disks shown in Examples 2 and 3 are almost the same as the results of Comparative Example 1 as shown in Table 2, that is, the cathodic arc evaporation method shown in Example 1 It was found that the magnetic properties were the same as those described above. Thus, also in the second and third embodiments, the above-described nitrogenated carbon film and silicon-containing carbon film are prevented from penetrating the recording magnetic film 4 by the cathodic arc vapor deposition process as the lower protective film. Turned out to be effective.

【００２６】この他にも下層保護膜には、炭素に少なく
とも水素、硼素、珪素、フッ素の何れかを含む薄膜材料
や、非磁性金属、又はその酸化物、窒化物、炭化物から
成る薄膜材料であってもよいが、エネルギー伝達関数に
示す通り、炭素原子との衝突により変換されるエネルギ
ーは、質量数が炭素原子に近いほど大きく、侵入が浅く
なり、薄くできるので有利である。また、炭素イオン入
射は下層保護膜内部の元素を上層保護膜内部にも拡散さ
せるため、下層保護膜としては炭素イオン入射による上
層保護膜の物性、構造への影響の少ない材料、又は、少
なくとも保護膜の性能を劣化させない材料の中から選ぶ
必要がある。In addition, the lower protective film is made of a thin film material containing at least hydrogen, boron, silicon, or fluorine in carbon, or a thin film material made of a nonmagnetic metal or an oxide, nitride, or carbide thereof. However, as shown in the energy transfer function, the energy converted by collision with carbon atoms is advantageous because the mass number is closer to the carbon atoms, the penetration is shallower, and the energy can be reduced. In addition, since carbon ion injection diffuses elements inside the lower protective film into the upper protective film, the lower protective film is made of a material that has little effect on the physical properties and structure of the upper protective film due to carbon ion injection, or at least protects the lower protective film. It is necessary to select from materials that do not degrade the performance of the film.

【００２７】［実施例４］本実施例では、比較例２の如
く、実施例１において保護膜を、カソーディック・アー
ク蒸着により炭素膜のみ２ｎｍの膜厚で記録磁性膜４上
に直接積層した。但し、本実施例では、カソーディック
・アーク蒸着の成膜工程で、成膜開始から一定時間だけ
基板に５０Ｖの正バイアスを印加した。本実施例では基
板に入射するイオン束により毎秒１平方センチメートル
あたり約１．２５ｘ１０16個の割合で炭素原子が堆積し
た。質量密度２．８ｇ・ｃｍ−３の炭素膜は約２．７ｘ
１０ 15個・ｃｍ−２の面密度で原子層が厚さ約０．１９
ｎｍに積層したと近似できるので、予想される成膜速度
は０．８９ｎｍ／秒となり、実測値と一致した。従っ
て、０．６秒で約０．５ｎｍの膜厚の初期成長層が形成
される。本実施例で基板に正バイアスを印加する時間は
０．７秒とした。本実施例によれば、下層保護膜５と上
層保護膜６の双方の形成を、カソーディック・アーク蒸
着法とそのバイアスの制御によって行うことができる。
そして、本実施例１と同様に、下層保護膜５により上層
保護膜６の形成時に炭素イオンが記録磁性膜４に侵入す
ることを防止することができ、磁気特性の優れた磁気記
録媒体を製造することができる。[Embodiment 4] In this embodiment, as in Comparative Example 2,
In the first embodiment, the protective film is
Only the carbon film is deposited on the recording magnetic film 4 with a thickness of 2 nm by vapor deposition.
Was directly laminated. However, in this embodiment, the cathodic
・ In the arc deposition process, only for a certain period of time from the start of film formation
A positive bias of 50 V was applied to the substrate. In this embodiment,
1 square centimeter per second depending on the ion flux incident on the plate
About 1.25x10 per16Carbon atoms are deposited
Was. A carbon film with a mass density of 2.8 gcm-3 is about 2.7x
10 FifteenAtomic layer thickness of about 0.19 with surface density of pcs.cm-2
Expected deposition rate
Was 0.89 nm / sec, which was in agreement with the actually measured value. Follow
0.6 seconds to form an initial growth layer with a thickness of about 0.5 nm
Is done. In this embodiment, the time for applying a positive bias to the substrate is
0.7 seconds. According to this embodiment, the lower protective film 5 is
The formation of both of the layer protective films 6 is performed by cathodic arc evaporation.
It can be performed by controlling the method of landing and the bias.
Then, similarly to the first embodiment, the lower protective film 5 forms an upper layer.
Carbon ions penetrate the recording magnetic film 4 when the protective film 6 is formed.
Magnetic recording with excellent magnetic properties.
Recording media can be manufactured.

【００２８】［実施例５］比較例２の如く、実施例１に
おいて保護膜を多層にせず、カソーディック・アーク蒸
着により炭素膜のみを２ｎｍの膜厚で記録磁性膜４上に
直接積層した。但し、本実施例では、カソーディック・
アーク蒸着の成膜工程で、成膜開始から０．７秒間だけ
エチレンガスを基板付近に導入した。Example 5 As in Comparative Example 2, only the carbon film was directly laminated on the recording magnetic film 4 to a thickness of 2 nm by cathodic arc deposition without using a protective film in multiple layers in Example 1. However, in this embodiment, cathodic
In the arc deposition film forming process, ethylene gas was introduced into the vicinity of the substrate for only 0.7 seconds from the start of film formation.

【００２９】[0029]

【表３】 [Table 3]

【００３０】実施例４及び実施例５の成膜工程により作
製された磁気ディスクの磁気特性を測定したところ、何
れも表３に示す如く比較例１での結果とほぼ一致した。
実施例４では、カソーディック・アーク蒸着の成膜工程
おいて、成膜開始から０．７秒間基板に印加した５０Ｖ
の正バイアスがイオンを減速して記録磁性膜４に到達し
た炭素イオンの侵入を阻止し、磁気特性の変動を防ぐの
に有効であった。一方、実施例５では、カソーディック
・アーク蒸着の成膜工程おいて、成膜開始から０．７秒
間基板付近に導入したエチレンガスの一部が励起、分解
されて炭化水素ラジカルとなって記録磁性膜４上に堆積
することで、カソーディク・アーク蒸着による炭素イオ
ンの記録磁性膜４への入射を阻止し、磁気特性の変動を
防ぐのに有効に作用した。When the magnetic characteristics of the magnetic disks produced by the film forming steps of Examples 4 and 5 were measured, the results were almost identical to those of Comparative Example 1 as shown in Table 3.
In the fourth embodiment, in the cathodic arc deposition film forming process, 50 V applied to the substrate for 0.7 seconds from the start of film formation.
The positive bias decelerated the ions and prevented the intrusion of the carbon ions reaching the recording magnetic film 4, which was effective in preventing the fluctuation of the magnetic characteristics. On the other hand, in Example 5, a part of ethylene gas introduced near the substrate for 0.7 seconds from the start of film formation was excited and decomposed and recorded as hydrocarbon radicals in the film formation process of cathodic arc evaporation. The deposition on the magnetic film 4 effectively prevented carbon ions from being incident on the recording magnetic film 4 by cathodic arc evaporation and prevented fluctuations in magnetic characteristics.

【００３１】[0031]

【発明の効果】以上のように、本発明によれば、カソー
ディック・アーク蒸着による炭素イオンの入射により、
ｓｐ３炭素比率が高く、緻密で硬い炭素保護膜を作製す
るにあたり、炭素イオンの記録磁性膜への侵入を阻止で
きるので、磁気特性を変化させることなく硬く耐蝕性と
耐摩耗性に優れた保護膜を備えた磁気記録媒体を製造す
ることができる。As described above, according to the present invention, by the injection of carbon ions by cathodic arc evaporation,
In producing a dense and hard carbon protective film having a high sp3 carbon ratio, it is possible to prevent carbon ions from entering the recording magnetic film, so that the protective film is hard and has excellent corrosion resistance and wear resistance without changing magnetic properties. Can be manufactured.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の特徴を最もよく表している磁気ディス
クの断面構成図FIG. 1 is a sectional configuration view of a magnetic disk that best illustrates the features of the present invention.

【図２】本発明の実施例及び比較例に示すアークイオン
ビーム蒸着装置の構成図FIG. 2 is a configuration diagram of an arc ion beam evaporation apparatus according to an embodiment of the present invention and a comparative example.

【図３】本発明の実施例に示すアークイオンビーム蒸着
装置を備えた磁気記ディスク製造設備の構成図FIG. 3 is a configuration diagram of a magnetic recording disk manufacturing facility including an arc ion beam evaporation apparatus according to an embodiment of the present invention.

【図４】本発明の比較例１に示す磁気記ディスクの断面
構成図FIG. 4 is a sectional configuration diagram of a magnetic recording disk shown in Comparative Example 1 of the present invention.

【図５】本発明の比較例２に示す磁気記ディスクの断面
構成図FIG. 5 is a cross-sectional configuration diagram of a magnetic recording disk according to Comparative Example 2 of the present invention.

【図６】本発明の実施例および比較例に示す磁気記録媒
体で測定したラマンスペクトルの比較FIG. 6 is a comparison of Raman spectra measured on magnetic recording media shown in Examples of the present invention and Comparative Examples.

【図７】本発明に係わる核阻止能計算によるＣｏ膜に入
射する炭素イオンと入射エネルギーの関係図FIG. 7 is a diagram showing the relationship between carbon ions incident on a Co film and the incident energy by nuclear stopping power calculation according to the present invention.

【図８】本発明に係わる核阻止能計算による炭素膜に入
射する炭素イオンと入射エネルギーの関係図FIG. 8 is a diagram showing a relationship between carbon ions incident on a carbon film and incident energy by nuclear stopping power calculation according to the present invention.

【図９】本発明の一実施例に示す試料のラマンスペクト
ル。FIG. 9 is a Raman spectrum of a sample shown in one example of the present invention.

【図１０】本発明の実施例２に示す磁気ディスクの断面
構成図FIG. 10 is a sectional configuration diagram of a magnetic disk according to a second embodiment of the present invention;

【図１１】本発明の実施例３に示す磁気ディスクの断面
構成図FIG. 11 is a sectional configuration diagram of a magnetic disk according to a third embodiment of the present invention;

【符号の説明】[Explanation of symbols]

１…ガラス製ディスク状基体、２…ＮｉＣｒ系プリコー
ド膜、３…Ｃｒ合金下地膜、４…ＣｏＣｒ系合金記録磁
性膜、５…緩衝膜、６…炭素保護膜、７…ローダー、８
a〜８ｆ…ゲート弁、９a〜９ｃ…マグネトロン・スパッ
タリング電極、１０…ヒーター、１１…カソーディック
・アーク蒸着装置、１２…アンローダー、１３… アー
クプラズマ源、１４… 成膜室、１５…ダクト、１６…
基板、１７a…電磁コイル（偏向コイル）、１７b…電磁
コイル（ソレノイドコイル）、１８…可動アノード、１
９…カソード、２０…アーク電源、２１…排気配管、２
２…アークプラズマビーム、２３…基板ホルダー、２４
…バイアス電源、２５…窒素化炭素保護膜、２６…炭素
膜、２７…比較例１でのラマンスペクトル、２８…実施
例１でのラマンスペクトル、２９…比較例２でのラマン
スペクトル、３０…窒素化炭素緩衝膜、３１…珪素含有
炭素緩衝膜DESCRIPTION OF SYMBOLS 1 ... Glass disk-shaped base, 2 ... NiCr pre-coding film, 3 ... Cr alloy base film, 4 ... CoCr-based alloy recording magnetic film, 5 ... Buffer film, 6 ... Carbon protective film, 7 ... Loader, 8
a to 8f: gate valve, 9a to 9c: magnetron sputtering electrode, 10: heater, 11: cathodic arc evaporation apparatus, 12: unloader, 13: arc plasma source, 14: film forming chamber, 15: duct, 16 ...
Substrate, 17a: electromagnetic coil (deflection coil), 17b: electromagnetic coil (solenoid coil), 18: movable anode, 1
9: cathode, 20: arc power supply, 21: exhaust pipe, 2
2 ... arc plasma beam, 23 ... substrate holder, 24
... Bias power supply, 25 ... Nitride carbon protective film, 26 ... Carbon film, 27 ... Raman spectrum in Comparative Example 1, 28 ... Raman spectrum in Example 1, 29 ... Raman spectrum in Comparative Example 2, 30 ... Nitrogen Carbon buffer film, 31 ... silicon-containing carbon buffer film

───────────────────────────────────────────────────── フロントページの続き (72)発明者 小角 雄一 神奈川県小田原市国府津2880番地 株式会 社日立製作所ストレージ事業部内 (72)発明者 大野 俊典 神奈川県小田原市国府津2880番地 株式会 社日立製作所ストレージ事業部内 Ｆターム(参考） 4K029 AA09 AA24 BA34 BA35 BA46 BA56 BA58 BB02 BD11 CA03 CA05 EA01 FA07 5D006 AA02 AA04 AA05 AA06 DA03 EA03 FA02 FA09 5D112 AA07 AA24 BC05 BC07 FA01 FB04 FB11    ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Yuichi Kosaku             2880 Kozu, Odawara City, Kanagawa Pref.             Hitachi, Ltd. Storage Division (72) Inventor Toshinori Ohno             2880 Kozu, Odawara City, Kanagawa Pref.             Hitachi, Ltd. Storage Division F term (reference) 4K029 AA09 AA24 BA34 BA35 BA46                       BA56 BA58 BB02 BD11 CA03                       CA05 EA01 FA07                 5D006 AA02 AA04 AA05 AA06 DA03                       EA03 FA02 FA09                 5D112 AA07 AA24 BC05 BC07 FA01                       FB04 FB11

Claims (11)

【特許請求の範囲】[Claims] 【請求項１】円板状の基材上に少なくとも下地膜、記録
磁性膜、保護膜を有する磁気記録媒体において、前記保
護膜が前記記録磁性膜上に形成された多層保護膜であっ
て、該多層保護膜の最上層が質量密度２．５ｇ・ｃｍ-3
以上の炭素膜であることを特徴とする磁気記録媒体。1. A magnetic recording medium having at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate, wherein the protective film is a multilayer protective film formed on the recording magnetic film, The uppermost layer of the multilayer protective film has a mass density of 2.5 g · cm −3.
A magnetic recording medium comprising the above carbon film. 【請求項２】請求項１記載の磁気記録媒体において、前
記多層保護膜の最上層を除く少なくとも一層が最上層よ
りも質量密度の低い厚さ０．２ｎｍ〜２ｎｍの炭素皮膜
であることを特徴とする磁気記録媒体。2. The magnetic recording medium according to claim 1, wherein at least one layer except the uppermost layer of the multilayer protective film is a carbon film having a lower mass density than the uppermost layer and a thickness of 0.2 nm to 2 nm. Magnetic recording medium. 【請求項３】請求項１記載の磁気記録媒体において、前
記多層保護膜の最上層を除く少なくとも一層が炭素に少
なくとも水素、窒素、硼素、珪素、フッ素の何れかを含
む厚さ０．２ｎｍ〜２ｎｍの皮膜から成ることを特徴と
する磁気記録媒体。3. The magnetic recording medium according to claim 1, wherein at least one layer of the multilayer protective film except for the uppermost layer contains at least one of hydrogen, nitrogen, boron, silicon and fluorine in carbon. A magnetic recording medium comprising a 2 nm film. 【請求項４】請求項１記載の磁気記録媒体において、前
記多層保護膜の最上層を除く少なくとも一層が珪素、又
はその酸化物、窒化物、炭化物、若しくは硼素、又はそ
の酸化物、窒化物、炭化物、若しくは非磁性金属、又は
その酸化物、窒化物、炭化物から成る厚さ０．２ｎｍ〜
２ｎｍの皮膜であることを特徴とする磁気記録媒体。4. The magnetic recording medium according to claim 1, wherein at least one layer except the uppermost layer of said multilayer protective film is silicon, or an oxide, nitride, carbide, or boron thereof, or an oxide, nitride thereof, Carbide, or non-magnetic metal, or an oxide, nitride, or carbide thereof having a thickness of 0.2 nm or more
A magnetic recording medium having a 2 nm film. 【請求項５】円板状の基材上に少なくとも下地膜、記録
磁性膜、保護膜を順次形成する工程を有する磁気記録媒
体の製造方法において、前記保護膜の形成工程が前記記
録磁性膜上に形成する多層保護膜の形成工程であり、該
多層保護膜の最上層の形成工程が、アークプラズマ源か
ら引き出された炭素イオンの入射により形成する工程で
あることを特徴とする磁気記録媒体の製造方法。5. A method for manufacturing a magnetic recording medium, comprising a step of sequentially forming at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate, wherein the forming of the protective film is performed on the recording magnetic film. Forming a multi-layered protective film, wherein the step of forming the uppermost layer of the multi-layered protective film is a step of forming by injecting carbon ions extracted from an arc plasma source. Production method. 【請求項６】請求項５記載の磁気記録媒体の製造方法に
おいて、前記多層保護膜の形成工程のうちの前記多層保
護膜の最上層を除く少なくとも一層の形成工程が、マグ
ネトロン・スパッタリング法、又はプラズマCVD法で厚
さ０．２ｎｍ〜２ｎｍの炭素皮膜を形成する工程である
ことを特徴とする磁気記録媒体の製造方法。6. The method of manufacturing a magnetic recording medium according to claim 5, wherein at least one of the steps of forming the multilayer protective film except for the uppermost layer of the multilayer protective film is performed by a magnetron sputtering method or A method for producing a magnetic recording medium, comprising a step of forming a carbon film having a thickness of 0.2 nm to 2 nm by a plasma CVD method. 【請求項７】請求項５記載の磁気記録媒体の製造方法に
おいて、前記多層保護膜の形成工程のうちの前記多層保
護膜の最上層を除く少なくとも一層の形成工程が、マグ
ネトロン・スパッタリング法、又はプラズマCVD法で炭
素で水素、窒素、硼素、珪素、フッ素の何れかを含む厚
さ０．２ｎｍ〜２ｎｍの皮膜を形成する工程であること
特徴とする磁気記録媒体の製造方法。7. The method of manufacturing a magnetic recording medium according to claim 5, wherein at least one of the steps of forming the multilayer protective film except for the uppermost layer of the multilayer protective film is performed by a magnetron sputtering method or A method for producing a magnetic recording medium, comprising a step of forming a film having a thickness of 0.2 to 2 nm containing any of hydrogen, nitrogen, boron, silicon, and fluorine with carbon by a plasma CVD method. 【請求項８】請求項５記載の磁気記録媒体の製造方法に
おいて、前記多層保護膜の形成工程のうちの前記多層保
護膜の最上層を除く少なくとも一層の形成工程が、マグ
ネトロン・スパッタリング法、又はプラズマCVD法で珪
素、又はその酸化物、窒化物、炭化物、若しくは硼素、
又はその酸化物、窒化物、炭化物、若しくは非磁性金
属、又はその酸化物、窒化物、炭化物から成る厚さ０．
２ｎｍ〜２ｎｍの皮膜を形成する工程であることを特徴
とする磁気記録媒体の製造方法。8. A method for manufacturing a magnetic recording medium according to claim 5, wherein at least one of the steps of forming the multilayer protective film except for the uppermost layer of the multilayer protective film is performed by a magnetron sputtering method or Silicon by plasma CVD method, or its oxide, nitride, carbide, or boron,
Or its oxide, nitride, carbide, or nonmagnetic metal, or its oxide, nitride, or carbide.
A method for producing a magnetic recording medium, which is a step of forming a film having a thickness of 2 nm to 2 nm. 【請求項９】円板状の基材上に少なくとも下地膜、記録
磁性膜、保護膜からなる磁気記録媒体の製造方法におい
て、前記記録磁性膜上に保護膜をアークプラズマ源から
引き出された炭素イオンの入射により形成する成膜工程
で、成膜開始から一定時間だけ基板に正バイアスを加え
ることを特徴とする磁気記録媒体の製造方法。9. A method for manufacturing a magnetic recording medium comprising at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate, wherein the protective film is formed on the recording magnetic film by a carbon drawn from an arc plasma source. A method for manufacturing a magnetic recording medium, wherein a positive bias is applied to a substrate for a certain period of time from the start of film formation in a film formation step formed by ion incidence. 【請求項１０】円板状の基材上に少なくとも下地膜、記
録磁性膜、保護膜からなる磁気記録媒体の製造方法にお
いて、前記記録磁性膜上に保護膜をアークプラズマ源か
ら引き出された炭素イオンの入射により形成する成膜工
程で、成膜開始から一定時間だけメタン、エタン、プロ
パン、ブタン、エチレン、プロピレン、ブチレン、アセ
チレン、トルエン等の炭化水素ガスを供給することを特
徴とする磁気記録媒体の製造方法。10. A method for manufacturing a magnetic recording medium comprising at least a base film, a recording magnetic film, and a protective film on a disk-shaped substrate, wherein the protective film is formed on the recording magnetic film by carbon drawn from an arc plasma source. Magnetic recording characterized by supplying a hydrocarbon gas such as methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, and toluene for a certain period of time from the start of film formation in a film formation step formed by ion injection. The method of manufacturing the medium. 【請求項１１】請求項１〜４のいずれか１つに記載の磁
気記録媒体を備えた磁気記憶装置。11. A magnetic storage device comprising the magnetic recording medium according to claim 1.
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